CHAPTER 18 - ELECTROCHEMISTRY Electrochemistry - a branch of chemistry that deals with the exploitation of spontaneous oxidationreduction reactions to obtain electrical

energy and the use of electrical energy to drive nonspontaneous reactions important in industrial extraction of certain elements. What you will be learning in this chapter? Draw diagrams representing electrochemical cell and write the cell notation; Know what reaction is taking place at the anode and cathode; Write equations for anode and cathode half-reactions and for the o!erall cell reaction; "alculate standard cell potentials #ocell from half-cell potentials #o; "alculate nonstandard cell potentials #cell using the $ernst equation; "alculate equilibrium constant %Kc& and standard free energy Go from #ocell. Know the different types of electrochemical cells and the difference between an electrochemical cells and an electrolytic cells; Know some important applications of electrochemical and electrolytic processes. "alculate amounts of products formed during electrolysis at anode and cathode.

18.1 Galvanic Cells ' gal!anic cell %also called !oltaic cell& is a de!ice that uses a spontaneous oxidation-reduction reaction to produce electric current. (he following are some examples of spontaneous oxidation-reduction reactions) *. 1. 2. 0. +#) nie) +#) nie) nie) +#) ,n%s& - "u./0%aq& "u%s& - ,n./0%aq& ,n%s& - "u1-%aq& "u%s& - ,n1-%aq& "r%s& - 2'g$/2%aq& "r%$/2&2%aq& - 2'g%s& "r%s& - 2'g-%aq& "r2-%aq& - 2'g%s& +n/0-%aq& - 34e1-%aq& - 56-%aq& +n1-%aq& - 34e2-%aq& - 061/%l& ,n%s& - 1+n/1%s& ,n/%s& - +n1/2%s&

7edox reactions can be broken into two half-reactions) #xample-*) /xidation half-reaction) ,n%s& ,n1-%aq& - 1e-

7eduction half-reaction) "u1-%aq& - 1 e- "u%s& /!erall reaction) ,n%s& - "u1-%aq& "u%s& - ,n1-%aq& #xample-1 /xidation half-reaction) 34e1-%aq& 34e2-%aq& - 3e-

7eduction half-reaction) +n/0-%aq& - 56-%aq& - 3e- +n1-%aq& - 061/%l& /!erall reaction) +n/0-%aq& - 34e1-%aq& - 56-%aq& +n1-%aq& - 34e2-%aq& - 061/%l&

 .pontaneous redox reactions are exothermic reactions. 6eat produced in an exothermic reaction is normally lost as heat. 6owe!er it can be trapped and con!erted into electrical energy if the reactants in!ol!ed are not in direct contact with each other. 8n gal!anic cells redox reactions is split into two halfreactions each occurring in two separate compartments called half-cells. (he chemical energy is used to dri!e electrons through the external circuit connecting the two half-cells thus producing electric current. 4or example consider the following reaction) ,n%s& - "u./0%aq& "u%s& - ,n./0%aq& 8f 9inc metal is placed in "u./ 0 solution an exothermic reaction occurs producing heat. 8n a gal!anic cell set up a 9inc metal is placed in ,n./ 0 solution in one container a copper metal in "u./ 0 solution in another container the two metals are connected by a wire and to complete the circuit the two solutions are connected by a :salt-bridge; containing strong electrolyte such as K"l %aq& or K1./0%aq& that allows ions to flow between the two half-cells. (he reactants - 9inc metal and copper ions are not allowed to come in direct contact. <ecause of the potential different between the two half-cells electrons are force to flow from the 9inc electrode %the anode& to the copper electrode %the cathode&. 't the interface between the 9inc electrode and ,n./0 solution ,n atoms are oxidi9ed to ,n 1- ions; while at the interface between copper electrode and "u./0 solution "u1- ions combine with incoming electrons and is reduced to "u atoms. (hese oxidation and reduction processes are shown in the following half-reaction equations) Anode-reaction %oxidation&) ,n%s& ,n1-%aq& - 1e-;

Cathode-reaction %reduction&) "u1-%aq& - 1e- "u%s& (he two half-cells are represented by notations ,n=,n 1- and "u1-="u. 8n a gal!anic cell the metal that is more readily oxidi9ed ser!es as an anode and the other as cathode. ,inc is more easily oxidi9ed than copper and it ser!es as the anode while copper forms the cathode. /xidation half-reaction occurs at anode and reduction half-reaction at cathode. (his gal!anic or !oltaic cell can be represented using the following cell notation) ,n|,n./0%aq&||"u./0%aq&|"u %' cell notation is always written with the anode on the left side and cathode on the right.& 't the anode half-cell ,n1- ions are continuously formed creating an excess of positi!e ions. While in the cathode half-cell "u1- ions are continuously reduced to "u causing a decrease in cation concentration. (o maintain electrically neutral solutions in both half-cells anions flow into the anode half-cell and cations flows into the cathode half-cell. (hus electric current is the flow of charged particles electrons flows from anode to cathode through wire; cations and anions flows in opposite direction through the salt-bridge . Cell Potential (he dri!ing force that enables electrons to flow from one electrode to the other is called electromotive force %emf& or cell potential % cell& which has the unit volt %>&. ' volt is one !oule per Coulomb where "oulomb is the unit of charge. 17.2 Stan a! Re "cti#n P#tential 8n a gal!anic cell electrons flow from one electrode to the other because there is an electrical potential difference between the two half-cells simply called the cell potential. 8n the 9inc-copper cell electrons flow from ,n=,n1- half-cell to "u="u1- half-cell. (he ,n=,1- half-cell has a higher electrical potential than "u="u 1-. (he magnitude of cell potential depends on the nature of the two half-cells the concentration of the

electrolyte in each half-cell and temperature. (he standard cell potential #ocell is the cell potential measured under standard conditions %* atm pressure for gas * + of electrolytes and at 13 o"&. (he standard half-cell potential or the reduction potential of a substance is determined by connecting the half-cell of the substance %under standard conditions& to the standard hydrogen electrode %.6#& as reference half-cell. (his reference half-cell consists of a ?t-electrode in a solution containing * + 6 - into which 61 gas is purged at a constant pressure of * atm. <ecause the reference half-cell is assigned 9ero potential the cell potential measured under this conditions is the standard half-cell potential of the substance. 4or example when a ,n=,n 1-%aq * +& half-cell is connected to the reference half-cell %.6#& the !oltage measured at 13 o" is found to be @.AB2 >. 6owe!er in this set up electron flows from ,n=,n 1- to :.6#; and relati!e to .6# the reduction potential for ,n=,n 1- half-cell will be the negati!e !alue of the measured !oltage. (hat is ,n1-%aq& - 1e- ,n%s&; 16-%aq& - 1e- 61%s&; "u1-%aq& - 1e- "u%s&;
o

C -@AB >; C @.@@@ > C @.20 >

%where

is the reduction potential&

.ince !alues are obtained against the standard hydrogen potential species with positi!e reduction potentials are easier to reduce compared to 6 - ions; while those with negati!e reduction potentials are more difficult to reduce. (herefore relati!e to 6 - "u1- is easier to reduce whereas ,n 1- is more difficult to reduce. When ,n=,n1- is connected to "u="u 1- half-cells the spontaneous process will be the flow of electrons from ,n= ,n1- to "u="u1- half-cell. 8n gal!anic cells species with more positi!e reduction potential ser!es as cathode and one with less positi!e or more negati!e reduction potential ser!es as the anode half-cell. (he net cell potential is the sum of the two half-cell potential. 4or the ,n-copper cell 'node half-cell reaction) ,n%s& ,n1-%aq& - 1e-;
o ,n D,n1"u1- D"u

C @.AB > C @.20 >

"athode half-cell reaction) "u1-%aq& - 1e- "u%s&; /!erall cell reaction) ,n%s& - "u1-%aq& ,n1-%aq& - "u%s&;
o cell

,n D,n1-

"u1- D"u

C @.AB > - @.20 > C *.*@ > 4or a cell consisting of "r="r2- and 'g='g- half-cells the cell notation and cell potential are) "r="r2-%aq * +&=='g-%aq * +&='g %anode& %cathode& 'node half-cell reaction) "r%s& "r2-%aq& - 2e-;
o "r D"r2'g- D'g

C @.A2 > C @.5@ >

"athode half-cell reaction) 'g-%aq& - e- 'g%s%aq&&; /!erall cell reaction) "r%s& - 2'g-%aq& "r2-%aq& - 2'g%s&;
o cell

"r "r2-

'g- 'g

C @.A2 > - @.5@ > C *.32 > EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE

#xercise-*) *. 4or each of the following gal!anic cell write the anode and cathode half-cell reactions the o!erall cell reaction and calculate the standard cell potential. Fse the standard reduction half-cell potentials gi!en in (able-*A.* %page 522& %a& ,n=,n1-%aq * +&==4e2- 4e1-%aq * +&=?t; %b& ,n=,n1-%aq * +&==<r1 <r-%aq * +&=?t; 1. Write the cell notation and calculate the standard cell potential for gal!anic cells in which the following reactions occur) %a& ?b%s& - 1 4e2-%aq& ?b1-%aq& - 14e1-%aq& %b& 1Gi%s& - 82-%aq& 1Gi-%aq& - 28-%aq& EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE 18.$ Cell P#tential an %!ee Ene!&' (he cell potential measures the potential difference between the two half-cells. ' potential difference of * > is equi!alent to * Houle of work done per "oulomb of charge that flows between two points in the circuit. %* > C * HI" or * H C * >."& +aximum work produced C charge x maximum potential Wmax C -"
max

C J
cell

#lectrical charge " C n#; J C -n#

; or Jo C -n#

cell

where n C mole of electrons transferred or that flow through circuit and # C KB 053 "Imol e- is called 4aradayLs constant 4or example the reaction) ,n%s& - "u1-%aq& ,n1-%aq& - "u%s& has (he standard free energy is Jo C -1 mol e- x
o cell

C *.*@ >

KB 053 " x *.*@ > C -1.*1 x *@3 H * mol e -

1.*1 x *@1 kH is the maximum work that can be deri!ed per mole of ,n reacted by "u 1-. #xercise-1) *. 8n the following reaction) ,n%s& - "u./0%aq& ,n./0%aq& - "u%s& What is the maximum energy produced when *3.@ g of ,n is completely reacted in a ,n-"u electrochemical cell that has an a!erage cell potential of *.@3 >? (he following reaction has an a!erage cell potential of 2.@@ >) 1 Gi %s& - Gi82 2 Gi8%aq& 6ow much energy can be deri!ed from a reaction in which 3.@@ g of Gi is oxidi9ed? EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE

1.

18.( )e*en ence #+ Cell P#tential #n C#ncent!ati#n (he quantitati!e relationship between electrolyte concentration and cell potential is gi!en by the following Nernst Equation)
cell

cell

- %7(In4& lnM;

is cell potential under non-standard conditions while ocell is cell potential under standard conditions %calculated from standard reduction potentials& 7 C 5.2*0 HI%mol.K& 4 C KB 053 "Imol is the 4aradayLs constant; M is the reaction quotient such that for the reaction)
cell

,n%s& - "u1-%aq& ,n1-%aq& - "u%s& 't 13 o"

$ C N,n1-OIN"u1-O.

%5.2*0 HImol.K&%1K5 K& 7( C C @.@13A HI" C @.@13A > KB 053 "Imol #

(he expression for the %ernst e"uation becomes

cell

C C

cell

%@.@13A >& ln$ ; n %@.@3K* >& log$ n

cell

4or example the non-standard cell potential for ,n=,n1-%aq @.@*@ +&=="u1-%aq *.@ +&="u can be calculated as follows)
cell

C%

"u1-="u

,n=,n1-

& - %@.@3K* >& log%N,n1-OIN"u1-O&; n

C %@.20 > - @.AB >& -

%@.@3K* >& log%@.@*@ +I*.@ +& n

C *.*@ > - @.@B@ > C *.*B > 4or the !oltaic cell "u="u1-%aq&=='g-%aq&='g the $ernst equation is expressed as)
cell

C%

'g-='g

"u="u1-

& - %@.@3K* >I1& log %N"u1-OIN'g-O1&

o cell

8f N'g-O C @.@*@ + N"u1-O C *.@ + and

cell

C @.5@ > P @.20 > C @.0B >

C @.0B > P C @.0B > P

%@.@3K* >& logQ*.@I%@.@*@&1R 1 %@.@3K* >& %0.@& C @.0B > P @.*1 > C @.20 > 1

(he cell potential calculated from $ernst equation is the maximum potential at the instant the cell circuit is connected. 's the cell discharges and current flows the electrolyte concentrations will change $ increases and cell deceases.

(he cell reaction will occur spontaneously until it reaches equilibrium at which point equilibrium constant& and
cell

$ C K %the

cell cell

- %7(In#& ln%K& C @ ; I7(; K C exp%n#

o cell

ln%K& C n#

I7(&

$ote also that at equilibrium G C Go P 7( ln%K& C @ %no current flows through the circuit& #xercise-2) *. Write an o!erall net ionic equation and calculate the cell potential at 13 o" for) ,n=,n1-%aq @.@@3@ +&||"u1-%aq *.@ +&="u 1. Write an o!erall net ionic equation and calculate the cell potential at 13 o" for) "u="u1-%aq @.@@3@ +&||'g-%aq @.3@ +&='g 2. (he standard cell potential %
1o cell 1-

& for the following gal!anic cell is *.*@ >

,n=,n %aq *+&||"u %aq *+&="u What is the K !alue for the reaction) ,n%s& - "u1-%aq& ,n1-%aq& - "u%s& ? Concentration Cells ' concentration cell is an electrochemical cell in which both half-cells are of the same type but with different electrolyte concentrations. (he following cell notations are examples of concentration cells) "u="u1-%aq @.@@*@ +&=="u1-%aq *.@ +&="u 'g='g-%aq @.@@*@ +& =='g-%aq @.*@ +&='g 8n concentration cells the half-cell with the lower electrolyte concentration ser!es as an anode half-cell and one with the higher electrolyte concentration is the cathode half-cell. 't the anode half-cell oxidation reaction occurs to increase the electrolyte concentration and at the cathode half-cell a reduction reaction occurs to decrease its electrolyte concentration. /xidation-reduction reaction will continue until the electrolyte concentrations in both half-cells become equal. 't anode half-cell) 't cathode half-cell) "u%s& "u1-%aq& - 1e-; %in @.@@*@ + "u1-& "u1-%aq& - 1e- "u%s&; %in @.3@ + "u1-&

#xercise-0) *. Determine the cell potentials of the following concentration cells) %a& "u="u1-%a" @.@@*@ +&=="u1-%aq *.@ +&="u %b& 'g='g-%a" @.@@*@ +&=='g-%aq @.*@ +&='g 1. ' concentration cell is set up by connecting a half-cell containing a 9inc electrode in @.*@ + ,n./ 0%aq& and another half-cell containing 9inc electrode in a saturated solution of ,n.. 8f the Ksp of ,n. is 1.3 x *@-11 what is the expected cell potential at 13o"? EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE

18., -atte!ies <atteries are gal!anic cells or a group of gal!anic cells connected in series where the total battery potential is equal to the sum of the potentials of the indi!idual cells. (here are three types of batteries P primary batteries secondary batteries and the fuel cell. ?rimary batteries are not re-chargeable where as secondary batteries are re-chargeable. 4uel cell will last as long as there is an ample supply of fuel to pro!ide the energy. Dry "ells) (he normal %acidic& dry batteries alkaline batteries and the mercury batteries are example of primary batteries. (he :acidic; dry battery consists of ,inc casing as container anode and as the reducing agent; graphite rod as %inert& cathode; aqueous $6 0"l paste as electrolyte and +n/1 powder as the oxidi9ing agent. ,n=,n1- $60- $62%aq&==+n1/2 +n/1="%s& 'node reaction) ,n%s& ,n1-%aq& - 1e-;

"athodic reaction) 1+n/1%s& - 1$60-%aq& - 1e- +n1/2%s& - 1$62%aq& - 61/%l& $et reaction) ,n%s& - 1+n/1%s& - 1$60-%aq& ,n1-%aq& - +n1/2%s& - 1$62%aq& - 61/%l& (he re!erse reaction is pre!ented by the formation of N,n%$6 2&0O1- ions. ' new dry cell battery has a potential of about *.3 > regardless of the si9e but the amount of energy that a battery can deli!er depends on its si9e. 4or example a D-si9e battery can deli!er more current %greater amperes& than an '''-si9e battery. $ormal dry batteries use aqueous $6 0"l paste as electrolyte and are referred to as acidic batteries due to the following ioni9ation) $6 0-%aq& $62%aq& - 6-%aq& Alkaline batteries also use 9inc %as the reducing agent& and +n/ 1 %as oxidi9ing agent& but aqueous paste containing K/6 instead of $60"l is used as the electrolyte. (he anode and cathode reactions are as follows) 't anode) ,n%s& - 1/6-%aq& ,n/%s& - 61/%l& - 1e-;

't cathode) 1+n/1%s& - 61/%l& - 1e- +n1/2%s& - 1/6-%aq&; $et reaction) ,n%s& - 1+n/1%s& ,n/%s& - +n1/2%s& .ince all reactants in!ol!ed are in the solid form alkaline batteries can deli!er a fairly constant !oltage until the limiting reactant is completely used up. (hey also last longer because 9inc metal corrodes more slowly under basic conditions. <atteries used in calculators and watches are mercury batteries. (he following reactions occur at the anode and cathode sections of the cell) 'node reaction) ,n%s& - 1/6-%aq& ,n/%s& - 61/ - 1e-; "athode reaction) 6g/%s& - 61/ - 1e- 6g%l& - 1/6-%aq& $et cell reaction) ,n%s& - 6g/%s& ,n/%s& - 6g%l&

Lead Storage atteries (hese are batteries used in all types of automobiles. (he lead storage batteries contain sulfuric acid as electrolyte. #ach cell contains a number of grids of lead alloy. /ne set of alternating grids is packed with lead metal and the other with lead%8>& oxide ?b/ 1. #ach set of grids which are the electrodes are connected in a parallel arrangement which enables the cell to deli!er more current - the amount of current deli!ered depends on the surface area of the electrode. #ach cell in a lead storage battery produces a potential of about 1.@* >. ' standard *1-> battery used in most cars contains six cells connected in series. .pontaneous 7eactions that occur in the lead storage battery are) 'node reaction) ?b%s& - 6./0-%aq& ?b./0%s& - 6-%aq& - 1e"athode reaction) ?b/1%s& - 26-%aq& - 6./0-%aq& - 1e- ?b./0%s& - 161/%m& $et reaction) ?b%s& - ?b/1%s& - 16-%aq& - 16./0-%aq& 1?b./0%s& - 161/%l& discharging (he greatest ad!antage of lead storage batteries is that they are re-chargeable. When you start the engine the discharge reaction occurs but while the car is being dri!en the battery obtains energy from the motor through the alternator and the following re-charging reaction occurs) 1?b./0%s& - 161/%l& ?b%s& - ?b/1%s& - 16-%aq& - 16./0-%aq& Gead storage batteries also ha!e a longer lifetime and can deli!er a relati!ely large amount of current and electrical energy within a short time. (he maSor disad!antages are) %*& they are !ery hea!y and bulky - nonportable; %1& lead is a toxic metal and the disposal creates en!ironmental problems; %2& the battery must be kept upright and 61./0 is !ery corrosi!e. Lit.i"/ 0atte!ies) these are batteries used in cameras and computers. 'node reaction) "athode reaction) $et cell reaction) 1 Gi%s& Gi-%aq& - 1e-; 82-%aq& - 1e- 28-%aq& 1Gi%s& - 82-%aq& 1Gi-%aq& - 28-%aq&

(he nic1el-ca /i"/ batteries are rechargeable batteries used in cordless phones. (hey contain cadmium as the anode and hydrated nickel oxide as the cathode. (he electrolyte is made up of aqueous K/6 paste. 'node reaction) "athode reaction) "d%s& - 1/6-%aq& "d%/6&1%s& - 1e-; 1$i/%/6&%s& - 161/%l& - 1e- 1$i%/6&1%s& - 1/6-%aq&;

$et cell reaction) "d%s& - 1$i/%/6&%s& - 161/%l& "d%/6&1%aq& - 1$i%/6&1%aq&; !uel Cells) ' fuel cell is a gal!anic cell that uses hydrogen %as fuel& which reacts with oxygen and a large amount of energy from the reaction is a!ailable to produce electricity. (he fuel is supplied continuously from an external tank. (he hydrogen-oxygen fuel cells are used in the space shuttle modules. 'node reaction) "athode reaction) 161%g& - 0/6-%aq& 061/%l& - 0e-; 161/%l& - /1%g& - 0e- 0/6-%aq&

$et cell reaction) 161%g& - /1%g& 161/%l& - #nergy EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE 18.2 C#!!#si#n C#nt!#l "orrosion is a spontaneous oxidation of metals by atmospheric oxygen P a process that has great economic impact. "onsider the rusting process of a steel pipe. (he process is accelerated by the presence of water droplets on the metal surface. 't the edge of the droplet the part of iron exposed to the air acts as the cathode for the electrochemical reaction. 't the center of the droplet the metal acts as anode and get oxidi9ed %corroded&.

/1

/6-

4e1- /6- /1 'node "athode

"athode

't the edge of the droplet molecular oxygen is reduced to /6 -) /1%g& - 161/%l& - 0e- 0/6-%aq& and at the center of the droplet metallic iron is oxidi9ed to 4e 1-) 14e%s& 14e1-%aq& - 0e8nside the droplets 4e1- combines with /6- to form iron%88& hydroxide 4e%/6& 1 which is then further oxidi9ed to iron%888& oxide 4e1/2.61/. 4e1-%aq& - 1/6 %aq& 4e%/6&1%s& 04e%/6&1%s& - /1%g& 14e1/2.61/%s& - 161/ TrustT "orrosion pre!ention can be done by passive method such as by painting the metal surface thus pre!ents contact of the metal surface with oxygen and moisture. (he acti!e method of corrosion pre!ention in!ol!es electrochemical process which is the method employed in the control of corrosion of underground steel pipes and tanks. 8f the pipe is wrapped or tied with a metal that is more electropositi!e than iron such as magnesium aluminum or 9inc then in electrochemical reactions these metals will act as the anodes and the iron %pipe& as the cathode while the wet soil acts as the electrolyte. (he sacrificial metals will be oxidi9ed before the pipe. 4or example if magnesium is used as sacrificial anode the following reactions will occur) 1+g%s& 1+g1-%aq& - 0e-; and /1%g& - 161/%l& - 0 e- 0/6-%aq& %at anode& %at cathode&
-

$et reaction) 1+g%s& - /1%g& - 161/ 1+g%/6&1%s&; (his method of corrosion pre!ention using acti!e metals such as magnesium as sacrificial anode is called a cathodic protection because as a cathode the pipe will not oxidi9ed. EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE

*@

**

18.7 Elect!#l'sis ' gal!anic cell produces current from a spontaneous oxidation-reaction. 'n electrolytic cell uses electrical energy to dri!e nonspontaneous oxidation-reduction reactions. Electrolysis in!ol!es forcing a current through a cell to produce a chemical change which has a negati!e cell potential. 4or example a lead storage or car battery is a gal!anic cell during the discharge process that is when you starts the car or when the headlight is on without the engine running. When the car is dri!en the re-charging reaction occurs and the battery acts as an electrolytic cell. 4or example the following spontaneous reaction occurs in a gal!anic cell that consists of ,n=,n1-%aq& and "u="u1-%aq& half-cells) ,n%s& - "u1-%aq& ,n1-%aq& - "u%s&; #ocell C *.*@ >

8n an electrolytic cell the re!erse reaction occurs if a !oltage greater than *.*@ > is applied. ' higher !oltage than #o is needed to cause the re!erse reaction; the excess !oltage is referred to as overpotential or overvoltage. (hree types of reactions are possible in electrolytic cells when a sufficient !oltage is applied) .olute ions or molecules may be oxidi9ed or reduced; (he sol!ent can be oxidi9ed or reduced; +etal electrode that forms the anode can be oxidi9ed.

Which of these reactions will actually take place depends both on the thermodynamic and kinetic properties of each reaction. 8n general the half-reactions with the most positi!e %or the least negati!e& reduction potential will occur before others. 8f the difference in the standard reduction potentials between two halfcell reactions is small concentration may determine the outcome of electrolysis. (his is a kinetic factor. 4or example the following reactions are possible during the electrolysis of * + $a"l %aq&) 't anode) 1"l-%aq& "l1%g& - 1e-; #o C -*.2B > 161/ /1%g& - 06-%aq& - 0e-; #o C -*.12 > 161/ - 1e- 61%g& - 1/6-%aq& $a-%aq& - e- $a%s&; #o C -@.52 > #o C -1.A* >

't cathode)

8n an actual electrolysis of aqueous sodium chloride "l 1 is formed at the anode instead of / 1 although #o for the formation of /1 from 61/ is less negati!e than for the formation of "l 1 from "l-. (his is because the formation of /1 in!ol!es a higher acti!ation energy %o!er!oltage& thus kinetically less fa!orable. 't the cathode 61 is formed since it requires less !oltage than the reduction of $a -%aq&. 8f a solution containing metal cations that require lower potential or one that has a positi!e reduction potential is electroly9ed the metal will be deposited on the cathode and no hydrogen will be produced. 4or example the electrolysis of aqueous copper%88& chloride solution will yield "l 1 gas at the anode and copper metal deposits at the cathode. 8f the anode is made of copper it will also be oxidi9ed because of the lower !oltage requirement relati!e to water. 'node reaction) "u%s& "u1-%aq& - 1e-; #o C -@.20 > #o C -@.20 >

"athode reaction) "u1-%aq& - 1e- "u%s&;

*1

Electrolysis of "ater (he decomposition of water is a nonspontaneous process which an amount of energy of about 0@@ kHImol of water. 6owe!er the decomposition of water can be effected by electrolysis in which oxygen is formed at the anode and hydrogen at the cathode) 'node reaction) 161/ /1 - 06-%aq& - 0e-; #o C -*.12 >

"athode reaction) 061/ - 0e- 161 - 0/6-%aq&; #o C -@.52 > $et reaction) B61/ 161 - /1 - 0%6- - /6-&; #o C -1.@B > 161/ 161 - /1; (his potential assumes an electrolytic cell with N6 -O C N/6-O C * + and ?61 C ?/1 C * atm. 8n the electrolysis of pure water where N6-O C N/6-O C *@-A + the potential for the o!erall process is P*.12 >. 6owe!er applying a !oltage of *.12 > will not be sufficient to affect the electrolysis of water. 'n extra !oltage of about * > %as overpotential or overvoltage& is needed to make the electrolysis takes effect. Electrolysis of Solution Containing #i$tures of %ons "onsider a solution containing "u 1- ,n1- and 'g- is electroly9ed using a current with sufficient !oltage to reduce all three cations. 8n such electrolysis the metal ha!ing the smallest potential will be the first to be formed. (he reduction potentials of these elements are as follows) 'g-%aq& - e- 'g%s&; "u1-%aq& - 1e- "u%s&; ,n1-%aq& - 1e- ,n%s&; #o C @.5@ > #o C @.20 > #o C -@.AB >

.ince the reduction of 'g - to 'g has the most positi!e potential sil!er will be deposited at the cathode before the other metals which is then followed by "u and ,n respecti!ely. 8f the !oltage supply is properly controlled starting with the lowest !oltage possible it is possible to separate the three metals using electrolysis. #xercise-3) *. What products are formed at the anode and cathode respecti!ely when each of the following solutions is electroly9ed? %a& Gi"l%aq& %c& $a"l%l& 1. %b& "u./0%aq& %d& 61./0%aq& using platinum as electrodes.

8n an electrolysis of a solution contains a mixture of 4e 1- "u1- and ?b1- ions in what order will the metals be deposited on the cathode? 8f the anode is a mixture of 4e "u and ?b in what order will they be oxidi9ed?

*2

&he Stoichiometry of Electrolysis ' &otal Charge and &heoretical (ield 'n electric current that flows through a cell is measured in ampere %A& which is the amount of charge in Coulomb %C& that flows through the circuit per second. (hat is 'mpere C "oulombIsecond %* A C * C3s& "oulomb C 'mpere x time in second %* C C * A.s& C total charge Houle C "oulomb x >olt %* 4 C * C.5& (he amount of substances formed at the anode or cathode can be calculated from the magnitude of current %in amperes& and time %in seconds& of electrolysis. 4or example if a current of *.3@ ' flows through an aqueous solution of "u./ 0 for 13.@ minutes the amount of charge passing through the solution is %*.3@ "Is&%13.@ minutes&%B@ secondsIminutes& C 113@ " (he number of moles of electrons passing through the solution C %113@ "& x %* mol e-E& KB 053 " C @.@122 mol .ince the reduction of "u1- requires 1 mol e- per mole of "u) "u1- - 1e- "u the amount of copper formed at the cathode is) %@.@122 mol e-& x %* mol "u& x %B2.33 g "u& C @.A0* g "u 1 mol e- * mol "u 8f the abo!e process uses a cell with a !oltage of 2.@ > the energy consumed is) 2.@ > x 113@ " C BA3@ ".> C B5@@ H C B.5 kH #xercise-B) *. 6ow many grams of sil!er will be produced if a current of *.3@ ' passes through a solution of 'g$/ 2 for 2@.@ minutes? 1. 6ow long %in minutes& would it take to deposit @.BA g of copper from a solution containing "u 1- using a cell that operates at B.@ > and produces a current of *.2 '? 6ow much energy %in kH& is consumed to produce this amount of copper?

18.8 C#//e!cial Elect!#l'tic P!#cesses (he production of acti!e metals such as sodium magnesium and aluminum from their compounds can only be accomplished by electrolysis which is carried out by passing current in the order of *@ 0 P *@3 'mperes. (he most common examples of this method of production are those of sodium magnesium and aluminum. .odium and magnesium are produced by electrolysis of molten sodium chloride and magnesium chloride respecti!ely.

*0

&he Production of Aluminum 'luminum is produced by electrolysis of molten 'l 1/2 in cryolite %$a2'l4B& in a process called the HallHe!#"lt *!#cess named after the founders. (he electrolytic cells for aluminum production use graphite for both anode and cathode. (he following reactions are thought to take place during the electrolysis which occurs at temperature abo!e *@@@ o") 't temperature abo!e *@@@ o" alumina reacts with molten cryolite ion) 'l1/2 - 0'l4B2- 2'l1/4B1- - B4-; (hen the anode and cathode reactions are thought to occur as follows) 'node reaction) "athode reaction) (he o!erall cell reaction is) 1'l1/4B1- - *14- - " 0'l4B2- - "/1 - 0e-; 'l4B2- - 2e- 'l - B4-; 'l1/2 - 2" 0'l - 2"/1%g&

(he anode which is made of graphite is consumed in the process and must be replaced from time to time. .ince aluminum is denser than aluminum oxide and cryolite the molten aluminum sinks to the bottom of the cell and can be remo!ed quite easily. (he aluminum produced in this process is about KK.3U pure. 'luminum forms strong but light construction materials when alloyed with 9inc or magnesium which are often used for making aircraft and aircraft engine. Electrolysis of #olten Salt to Produce Sodium (he electrolysis of molten salt to produce sodium metal is commercially carried out in the )#6ns cells at temperature around B@@ o". "hlorine is a by-product in this process. 't the anode) 't the cathode) $et reaction) 1 "l
-

"l1%g& - 1e-

1$a- - 1e- 1$a%l& 1$a"l%l& 1$a%l& - "l1%g&

8n the Downs cells the anode and cathode chambers are separated by a steel screen to pre!ent contact between molten sodium metal and chlorine gas to pre!ent an explosi!e reaction between the two reacti!e elements. (he molten sodium metal forms a layer abo!e the molten $a"l and can be siphoned off. (o obtain sodium metal the electrolysis must use molten $a"l to which <a"l 1 is added to lower the melting point. 8f aqueous $a"l is used water will be reduced at the cathode and hydrogen gas instead of sodium is produced. Electrolysis of rine Solution for Commercial Production of Sodium )ydro$ide .odium hydroxide is commercially produced by electrolysis of brine solution %saturated salt solution in the chlor-alkali process. 'node reaction) 1"l %aq& "l1%g& - 1e-;
-

"athode reaction) 161/ - 1e- 61%g& - 1/6 %aq&; $et reaction) 1$a"l%aq& - 161/ 1$a/6%aq& - 61%g& - "l1%g& (he !oltage requirement for the reduction of $a- is higher than that required for reducing water. (hus hydrogen gas is produced instead of sodium metal. /xygen gas is not formed at the anode because it

*3

in!ol!es a high o!er!oltage compared to that for chlorine gas. 's a result the o!erall !oltage requirement to oxidi9e water %which will produce oxygen gas& is greater than the o!erall potential needed to produce chlorine gas. Electro-refining of Copper #lectrolysis is also an important process in the purification of some metals. 4or example impure copper from the chemical reduction of copper ore is cast into large slabs that ser!e as the anodes for electrolytic cells. (he cells also use thin sheets of ultra pure copper as cathodes and aqueous copper%88& sulfate as the electrolyte. 'ssuming 9inc and iron as the maSor impurities in the copper slabs the following reactions occur at the anode) ,n ,n1-%aq& - 1e-; #o C @.AB > 4e 4e1-%aq& - 1e-; "u "u1-%aq& - 1e-; #o C @.00 > #o C -@.20 >

<y maintaining a low !oltage supply only copper is deposited at the cathode which is made of pure copper metal sheet; ionic impurities remain in solution. Electroplating ?lating a thin coating of a metal that resist corrosion can protect other metals that readily corrode. (he process is called electroplating in which the corrosion resistant metal is used as the anode where it is oxidi9ed and goes into solution. (he ions formed from this metal are then reduced at the cathode which consists of utensils to be electroplated. (he electrolyte usually contains a low ion concentration of electroplating metal. 4or example in silver plating sil!er metal is used as the anode and the utensil to be sil!er-plated as the cathode; the electrolyte consists of 'g$/ 2 in K"$%aq&. 8n solution 'g- forms complex with "$'g-%aq& - 1"$ %aq& 'g%"$&1-%aq&; (his reaction maintains a !ery low concentration of free 'g - ion in solution and yields a !ery thin and uniform sil!er coating. 'node reaction) "athode reaction) 'g - 1"$ %aq& 'g%"$&1 %aq& - e-; 'g%"$&1 %aq& - e- 'g%s& - 1"$ %aq&;
-

#xercise-A) *. 6ow many grams of $a and "l1 respecti!ely can be produced in *.@@ hr by the electrolysis of molten $a"l in a Downs cell that operates at 3.@ > and A.3 x *@ 0 amperes? 6ow many kilowatt-hours %kWh& of energy are consumed to produce this amount of sodium and chlorine? %4aradayLs constant C KB 053 "Imol e-; * kWh C 2.B x *@B H& 1. (he electrolysis of 'l1/2 in molten cryolite to produce aluminum metal uses a cells that operate at 0.3 > and 1.@ x *@3 '. 6ow long does it take to produce K@5 kg %V * ton& of aluminum? 6ow much kWh of energy is consumed to produce this much aluminum? %4aradayLs constant C KB 053 "Imol e -; * kWh C 2.B x *@B H&

*B

2.

+olten magnesium chloride is electroly9ed in a cell that operates at 0.3 > and *.3 x *@ 3 '. 6ow many kilograms of magnesium are produced in an 5.@-hour shift? What other product is also formed and on which electrode? %4aradayLs constant C KB 053 "Imol e-; * kWh C 2.B x *@B H&

EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE

*A